Inhibition of catalytic oxidation of carbon/carbon composites by phosphorus

Xianxian Wu, Ljubisa R. Radovic

Research output: Contribution to journalArticle

118 Citations (Scopus)

Abstract

The inhibition effectiveness of thermally deposited phosphorus (P) compounds on the carbon oxidation catalyzed by potassium or calcium acetate has been investigated. The P deposit was formed by impregnating carbon/carbon composite samples with methanol solution of methyl-phosphoric acid or phosphorus oxychloride and heating at ca. 600 °C. An amorphous layer formed by a relatively large amount of P deposit functioned as a barrier for the access of the catalyst to the carbon surface even though it had almost no barrier effect for O2 access. The catalytic effect of calcium was almost completely suppressed by such deposit, but the effect of potassium was only partially suppressed due to the superior wetting ability and mobility of potassium species. Small amounts of P deposit showed similar inhibition effects on non-catalyzed oxidation, while their effects on catalytic oxidation were not as good. Characterization of P-deposited carbon samples by XPS, XRD, SEM and TPD, as well as ab initio MO calculations, suggested that the inhibition effect mainly resulted from the formation of oxygen-containing P groups which may include metaphosphates, C-O-PO3 groups and C-PO3 groups. Those groups are suggested to act as a physical barrier against carbon/catalyst interfacial contact as well as to block the active carbon sites. The presence of bridge oxygen bonded to a carbon site and a P group appears to be a critical factor for maintaining the inhibition effect. Indeed, the loss of such oxygen or connecting bond seems to result in loss of inhibition.

Original languageEnglish (US)
Pages (from-to)141-151
Number of pages11
JournalCarbon
Volume44
Issue number1
DOIs
StatePublished - Jan 1 2006

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Carbon carbon composites
Catalytic oxidation
Phosphorus
Carbon
Deposits
Potassium
calcium acetate
Oxygen
Calcium
Potassium Acetate
Oxidation
Catalysts
Phosphoric acid
Temperature programmed desorption
Methanol
Wetting
X ray photoelectron spectroscopy
Heating
Scanning electron microscopy

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Materials Science(all)

Cite this

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abstract = "The inhibition effectiveness of thermally deposited phosphorus (P) compounds on the carbon oxidation catalyzed by potassium or calcium acetate has been investigated. The P deposit was formed by impregnating carbon/carbon composite samples with methanol solution of methyl-phosphoric acid or phosphorus oxychloride and heating at ca. 600 °C. An amorphous layer formed by a relatively large amount of P deposit functioned as a barrier for the access of the catalyst to the carbon surface even though it had almost no barrier effect for O2 access. The catalytic effect of calcium was almost completely suppressed by such deposit, but the effect of potassium was only partially suppressed due to the superior wetting ability and mobility of potassium species. Small amounts of P deposit showed similar inhibition effects on non-catalyzed oxidation, while their effects on catalytic oxidation were not as good. Characterization of P-deposited carbon samples by XPS, XRD, SEM and TPD, as well as ab initio MO calculations, suggested that the inhibition effect mainly resulted from the formation of oxygen-containing P groups which may include metaphosphates, C-O-PO3 groups and C-PO3 groups. Those groups are suggested to act as a physical barrier against carbon/catalyst interfacial contact as well as to block the active carbon sites. The presence of bridge oxygen bonded to a carbon site and a P group appears to be a critical factor for maintaining the inhibition effect. Indeed, the loss of such oxygen or connecting bond seems to result in loss of inhibition.",
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Inhibition of catalytic oxidation of carbon/carbon composites by phosphorus. / Wu, Xianxian; Radovic, Ljubisa R.

In: Carbon, Vol. 44, No. 1, 01.01.2006, p. 141-151.

Research output: Contribution to journalArticle

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